Selective Photoinduced α‐Amino C(sp 3 )–H Alkylation Mediated by NHC–Borane

Herein, we report a selective photoinduced functionalization of α‐amino C(sp 3 )─H bonds mediated by NHC–boranes. This reaction proceeds efficiently without the need for any external radical initiator or photoredox catalyst. Mechanistic studies reveal that the reaction proceeds via an efficient radical chain, featuring the formation of an aryl radical driven by a boryl‐mediated XAT and a subsequent 1,5‐HAT as key steps. The method demonstrates broad functional group tolerance, providing a practical route for the synthesis of nitrogen‐containing molecules.